JP7076113B2 - Formic acid production method and formic acid production system - Google Patents
Formic acid production method and formic acid production system Download PDFInfo
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- 235000019253 formic acid Nutrition 0.000 title claims description 125
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 title claims description 122
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/295—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with inorganic bases, e.g. by alkali fusion
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J19/12—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electromagnetic waves
- B01J19/122—Incoherent waves
- B01J19/127—Sunlight; Visible light
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
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- B01J35/23—
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- B01J35/39—
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
- B01J8/06—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds in tube reactors; the solid particles being arranged in tubes
- B01J8/065—Feeding reactive fluids
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B61/00—Other general methods
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J2219/0873—Materials to be treated
- B01J2219/0892—Materials to be treated involving catalytically active material
Description
本発明は、太陽光を利用して有機物質から蟻酸を生成する蟻酸生成方法及び蟻酸生成システムに関する。 The present invention relates to a formic acid production method and a formic acid production system for producing formic acid from an organic substance using sunlight.
水素を燃料として利用する「水素社会」のアイデアは以前から提案されているが、水素を貯蔵・運搬することの難しさやエネルギー変換効率の点から現在でも普及するに至っているとは言い難い。例えば、エネルギー密度の低い水素を自動車の燃料として持ち運ぶには、数百気圧もの高圧をかけなければならない。液体水素にする方法もあるが、超低温にする必要があるため、一般的ではない。そこで、蟻酸（ＨＣＯＯＨ）を水素源の中間物質として生成し、貯蔵する技術が研究されている。蟻酸は常温で液体であり、エネルギー密度も高いため、貯蔵物質として優れている。 The idea of a "hydrogen society" that uses hydrogen as a fuel has been proposed for some time, but it is hard to say that it has become widespread even now due to the difficulty of storing and transporting hydrogen and the energy conversion efficiency. For example, in order to carry hydrogen, which has a low energy density, as fuel for automobiles, high pressure of several hundred atmospheres must be applied. There is also a method of using liquid hydrogen, but it is not common because it requires ultra-low temperature. Therefore, a technique for producing and storing formic acid (HCOOH) as an intermediate substance of a hydrogen source is being studied. Formic acid is a liquid at room temperature and has a high energy density, so it is an excellent storage substance.
例えば、特許文献１において、人工光合成において色素分子の励起エネルギーを奪うことなく、メチルビオローゲンへの電子移動を達成することができ、効率的に水素源を蟻酸に変換して貯蔵することができる蟻酸生成デバイスが提案されている。
For example, in
すなわち、特許文献１に係る発明は、基板の表面に形成した酸化アルミニウム微粒子による多孔質層に色素、メチルビオローゲン、及び蟻酸脱水素酵素を担持させてなる蟻酸生成デバイスである。酸化アルミニウム微粒子は色素分子の励起エネルギーを奪うことがないため、効率的にメチルビオローゲンへの電子移動を達成することができ、水素源を蟻酸に変換して貯蔵することができる。
That is, the invention according to
しかしながら、特許文献１に係る発明では、補酵素等（メチルビオローゲン）を必要とするため、コスト面や効率面で十分とは言えない面があった。
However, since the invention according to
自然エネルギーとして太陽光を活用し、比較的安定した有機物質から活性度の高い有機物を生成することは、薬品製造から輸送燃料や発電に至る多くの分野において、人類が今のうちに獲得しておくべき重要な技術であり、このような人工光合成手法は、その確立とより効率的な収率が希求されている。 Utilizing sunlight as natural energy to produce highly active organic matter from relatively stable organic matter has been acquired by humankind in many fields from chemical manufacturing to transportation fuel and power generation. It is an important technique to be kept, and such an artificial photosynthesis method is sought after for its establishment and more efficient yield.
このような状況から、化学エネルギーとして水素に比較的容易に転換可能であり、かつ人類にとって有用な化学物質である蟻酸生成を太陽光エネルギーを使って行える手段を、低コストで提供することが必要とされている。 Under these circumstances, it is necessary to provide a means at low cost that can be converted to hydrogen as chemical energy relatively easily and that formic acid, which is a useful chemical substance for humankind, can be produced using solar energy. It is said that.
本発明は、このような状況を鑑みてなされたものであり、低コストでかつ生成効率の高い蟻酸生成方法及び蟻酸生成システムを提供することを目的とする。 The present invention has been made in view of such a situation, and an object of the present invention is to provide a formic acid production method and a formic acid production system at low cost and with high production efficiency.
本発明の一態様は、有機物質を含む溶液と光触媒機能を有する金属酸化物粉末を混合する工程と、有機物質と金属酸化物粉末の混合溶液に対して太陽光又は光を照射して反応させる工程と、反応後の前記混合溶液から蟻酸を回収する工程を有し、混合溶液は炭素パウダーを含むことを特徴とする蟻酸生成方法である。 One aspect of the present invention is a step of mixing a solution containing an organic substance and a metal oxide powder having a photocatalytic function, and irradiating a mixed solution of the organic substance and the metal oxide powder with sunlight or light to cause a reaction. It is a method for producing formic acid , which comprises a step and a step of recovering formic acid from the mixed solution after the reaction, wherein the mixed solution contains carbon powder .
本発明の一態様によれば、有機物質と光触媒機能を有する金属酸化物粉末という必要最小限の組み合わせによって低コストでかつ高い生産効率で蟻酸を生成することができる。 According to one aspect of the present invention, formic acid can be produced at low cost and with high production efficiency by the minimum necessary combination of an organic substance and a metal oxide powder having a photocatalytic function.
このとき、本発明の一態様では、金属酸化物粉末は、酸化チタン又は酸化亜鉛としてもよい。 At this time, in one aspect of the present invention, the metal oxide powder may be titanium oxide or zinc oxide.
酸化チタン又は酸化亜鉛が蟻酸生成の光触媒として優れた効果を奏する。 Titanium oxide or zinc oxide exerts an excellent effect as a photocatalyst for formic acid production.
また、本発明の一態様では、有機物質は色素を含むとしてもよい。 Further, in one aspect of the present invention, the organic substance may contain a dye.
色素を用いることで蟻酸生成速度を向上させることができる。 The rate of formic acid production can be improved by using a dye.
また、本発明の一態様では、混合溶液中に、金属酸化物粉末濃度が８～１８％、色素濃度が０．０２～０．１１％で含まれているとしてもよい。 Further, in one aspect of the present invention, the mixed solution may contain a metal oxide powder having a concentration of 8 to 18% and a dye concentration of 0.02 to 0.11%.
金属酸化物粉末濃度と色素濃度をそれぞれ上記範囲内とすることで高い蟻酸生成速度を実現することができる。 A high formic acid production rate can be realized by setting the metal oxide powder concentration and the dye concentration within the above ranges, respectively.
また、本発明の一態様では、有機物質は植物由来のものを含むとしてもよい。 Further, in one aspect of the present invention, the organic substance may include those derived from plants.
例えば、落ち葉や廃材等の廃棄植物を蟻酸生成の原料として利用すれば、環境にも良い蟻酸生成方法となる。 For example, if waste plants such as fallen leaves and waste materials are used as raw materials for formic acid production, it becomes an environmentally friendly formic acid production method.
また、本発明の一態様では、混合溶液を循環させ、該混合溶液に太陽光を照射することによって蟻酸の生成反応を行うとしてもよい。 Further, in one aspect of the present invention, the mixed solution may be circulated and the mixed solution may be irradiated with sunlight to carry out a formic acid production reaction.
このようにすることで、人工光合成に必要な材料が水中を撹拌されながら動くので、均一に太陽光が当たり、蟻酸生成の効率が高くなる。 By doing so, the material required for artificial photosynthesis moves while being agitated in the water, so that the sunlight is uniformly applied and the efficiency of formic acid production is increased.
本発明の他の態様は、有機物質を含む溶液と光触媒機能を有する金属酸化物粉末を投入する原料投入部と、有機物質と金属酸化物粉末の混合溶液に対して太陽光又は光を照射して反応させる人工光合成反応部と、反応後の混合溶液から蟻酸を回収する蟻酸回収部を備え、混合溶液は炭素パウダーを含むことを特徴とする蟻酸生成システムである。 In another aspect of the present invention, a raw material charging section for charging a solution containing an organic substance and a metal oxide powder having a photocatalytic function, and a mixed solution of the organic substance and the metal oxide powder are irradiated with sunlight or light. It is an formic acid generation system characterized by comprising an artificial photosynthetic reaction section for reacting with the above and an formic acid recovery section for recovering formic acid from the mixed solution after the reaction, and the mixed solution contains carbon powder .
本発明の他の態様によれば、簡易な構成とすることができるので、低コストでメンテナンスも容易な蟻酸生成システムを提供することができる。 According to another aspect of the present invention, since the configuration can be simplified, it is possible to provide a formic acid generation system which is low in cost and easy to maintain.
また、このとき、本発明の他の態様では、人工光合成反応部は、光を透過するチューブ状ないし任意形状の筒状の部材であって、建物の屋根又は屋上に敷設され、混合溶液を部材内で循環させることにより人工光合成反応を行うとしてもよい。 Further, at this time, in another aspect of the present invention, the artificial photosynthesis reaction unit is a tubular member having a tubular shape or an arbitrary shape that transmits light, and is laid on the roof or roof of the building to form a mixed solution. The artificial photosynthesis reaction may be carried out by circulating in the inside.
このような構成とすることにより、例えば、住宅の屋根又は屋上に設置することで、日中の太陽光を利用して蟻酸を生成し、ひいてはその蟻酸からエネルギーとしての水素を発生させることができる。 With such a configuration, for example, by installing it on the roof or rooftop of a house, it is possible to generate formic acid by utilizing the sunlight in the daytime, and by extension, hydrogen as energy can be generated from the formic acid. ..
以上説明したように本発明によれば、低コストでかつ生成効率の高い蟻酸生成方法及び蟻酸生成システムを提供することができる。 As described above, according to the present invention, it is possible to provide a formic acid production method and a formic acid production system at low cost and with high production efficiency.
以下、本発明の好適な実施の形態について図面を参照しながら詳細に説明する。なお、以下に説明する本実施形態は、特許請求の範囲に記載された本発明の内容を不当に限定するものではなく、本実施形態で説明される構成の全てが本発明の解決手段として必須であるとは限らない。 Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings. It should be noted that the present embodiment described below does not unreasonably limit the content of the present invention described in the claims, and all the configurations described in the present embodiment are indispensable as the means for solving the present invention. It is not always the case.
人工光合成による水素の発生には主に二つの方法がある。第一は、酸化チタンと色素など各種材料をフィルム状に塗布して、光を当てて蟻酸をつくり、その蟻酸にプラチナ触媒等を付与して水素を発生させる方法であり、第二は、酸化チタンに触媒を入れ、太陽光を当てて水から直接水素を発生させる方法である。両者は、人工光合成研究として、水素発生を主たる目的として、鋭意研究開発に取り組んでいる状況にある。 There are two main methods for generating hydrogen by artificial photosynthesis. The first is a method in which various materials such as titanium oxide and a dye are applied in the form of a film and exposed to light to produce formic acid, and a platinum catalyst or the like is applied to the formic acid to generate hydrogen, and the second is oxidation. This is a method in which a catalyst is placed in titanium and exposed to sunlight to generate hydrogen directly from water. Both of them are working diligently on research and development as artificial photosynthesis research with the main purpose of hydrogen generation.
例えば、上述した特許文献１のように、これまでに、二酸化炭素・色素・酸化チタン光触媒に太陽光を照射することで、蟻酸を生成する方法が考案されている。しかしながら、その生成量は現時点では極めて少量であり、かつ色素も壊れにくい高価な材料が必要であるため、より実用性の高いシステムが必要とされている。
For example, as in
従来の知見では、光触媒として酸化チタン等とビオローゲンと色素を溶液ないし膜として製作し、光を当てることで蟻酸が生成されていた。しかし、ビオローゲンと色素はこの反応に必須の材料ではなく、炭素を含む有機物質を光触媒に混ぜることで、人工光合成反応が進み、蟻酸が生成されることが分かった。 According to the conventional knowledge, formic acid is produced by producing titanium oxide or the like, viologen, and a dye as a solution or a film as a photocatalyst and irradiating them with light. However, it was found that biologens and dyes are not essential materials for this reaction, and that by mixing an organic substance containing carbon with a photocatalyst, the artificial photosynthesis reaction proceeds and formic acid is produced.
すなわち、本発明の一態様は、有機物質を含む溶液に、光触媒機能を有する金属酸化物粉末を混合して混合溶液とし、該混合溶液に光照射することで蟻酸を生成させることを特徴とする蟻酸生成方法である。 That is, one aspect of the present invention is characterized in that a solution containing an organic substance is mixed with a metal oxide powder having a photocatalytic function to form a mixed solution, and formic acid is generated by irradiating the mixed solution with light. It is a method for producing formic acid.
有機物質は炭素原子を含むものであれば、特に限定はされない。図１及び図２に各種有機物質材料の蟻酸生成速度比を示す。有機物質は、光反応を助ける役割を果たす色素を含むものが好ましいが、色素のない有機物質であっても適用可能である。一例としてアントシアニンＢ（紫キャベツに含まれる色素）を基準とした場合に、図１に示すようにイノシトール（ビタミンＢ群の一種）やブドウ糖（自然界に最も多く存在する単糖類）などは、アントシアニンＢと同等の蟻酸生成速度比を有する。また、アントシアニンＢよりは蟻酸生成速度が劣るがデキストリン、セロビオース、セルロース等の二糖類や多糖類も本発明に適用可能である。糖類（単糖類、二糖類、多糖類）については、還元性を有するものを用いることが好ましい。 The organic substance is not particularly limited as long as it contains a carbon atom. 1 and 2 show the formic acid production rate ratios of various organic substances. The organic substance preferably contains a dye that plays a role in assisting the photoreaction, but an organic substance without a dye can also be applied. As an example, based on anthocyanin B (pigment contained in purple cabbage), as shown in FIG. 1, inositol (a type of vitamin B group) and glucose (a monosaccharide most abundant in nature) are anthocyanin B. Has an anthocyanin production rate ratio equivalent to that of. In addition, disaccharides and polysaccharides such as dextrin, cellobiose, and cellulose, which have a lower rate of formic acid production than anthocyanin B, can also be applied to the present invention. As the saccharide (monosaccharide, disaccharide, polysaccharide), it is preferable to use one having a reducing property.
また、有機物質は、図２に示すように、植物、落ち葉、野菜、果物等であってもよい。落ち葉等の廃棄植物や、生ごみ等の廃棄食物を蟻酸生成の原料として利用すれば、環境にも良い蟻酸生成方法を実現することができる。これらの廃材を利用する際には、適宜、酸又は塩基を添加し、加熱処理を行うことで蟻酸生成量や蟻酸生成速度が向上する場合がある。また、図２に示すように、有機物質として糖蜜を採用することもできる。糖蜜は、例えば、サトウキビやテンサイを精製した際に生じる廃糖蜜を有効利用してもよい。 Further, as shown in FIG. 2, the organic substance may be a plant, fallen leaves, vegetables, fruits and the like. If waste plants such as fallen leaves and waste foods such as swill are used as raw materials for formic acid production, an environmentally friendly formic acid production method can be realized. When using these waste materials, the amount of formic acid produced and the rate of formic acid production may be improved by appropriately adding an acid or a base and performing a heat treatment. Further, as shown in FIG. 2, molasses can also be adopted as an organic substance. As the molasses, for example, the molasses produced when sugar cane or sugar beet is refined may be effectively used.
有機物質は、色素を有しないブドウ糖単独でも良いが、色素と組み合わせることにより、蟻酸生成速度を大きく向上させることができる。色素としては、緑色素、クチナシ赤、マーキュロクロムを組み合わせることで、蟻酸生成速度が大きく向上することを確認したが、それ以外の色素であってもよい。 The organic substance may be glucose alone without a pigment, but by combining it with a pigment, the rate of formic acid production can be greatly improved. As the dye, it was confirmed that the formic acid production rate was greatly improved by combining green dye, gardenia red, and mercurochrome, but other dyes may be used.
あるいは、色素に変えて、炭素パウダーを用いてもよい。炭素パウダーとしては、例えば活性炭パウダーが用いられる。後述する実施例でも示されているように、炭素パウダーを用いることにより、色素と同等又はそれ以上の蟻酸生成速度を実現することができる。また、炭素パウダーを用いた場合には、紫外線を単独で照射した後の光照射で蟻酸生成速度が向上する傾向があることが判明した。 Alternatively, carbon powder may be used instead of the dye. As the carbon powder, for example, activated carbon powder is used. As shown in the examples described later, the use of carbon powder can realize a formic acid production rate equal to or higher than that of the dye. Further, it was found that when carbon powder was used, the formic acid production rate tended to be improved by light irradiation after irradiation with ultraviolet rays alone.
蟻酸生成速度は、混合溶液中の金属酸化物粉末や色素の濃度によっても変化する。後述する実施例でも示しているが、一例として、グルコース（ブドウ糖）からの蟻酸生成においては、金属酸化物粉末（酸化チタン）濃度が８～１８％、色素（緑色素）濃度が０．０２～０．１１％の時に高い蟻酸生成速度を有する。 The rate of formic acid formation also changes depending on the concentration of the metal oxide powder or dye in the mixed solution. As shown in Examples described later, as an example, in the production of formic acid from glucose (dextrose), the concentration of the metal oxide powder (titanium oxide) is 8 to 18%, and the concentration of the dye (green pigment) is 0.02 to. It has a high formic acid production rate at 0.11%.
金属酸化物粉末は光触媒機能を有するものであれば特に限定はされない。図３は、各種金属酸化物についての蟻酸生成量を比較した図である。図３に示すように、特に酸化チタン又は酸化亜鉛を用いることが好ましい。これらの金属酸化物は、混合溶液中での接触表面積を増加させるために、微粒子の状態となっていることが好ましい。微粒子の平均粒径は、特に限定されるわけではないが、一例としては、２０～５０ｎｍである。特に酸化チタン微粒子の平均粒径は２５ｎｍ程度とすることが好ましい。また、酸化チタンのうち、アナターゼ型がルチル型に比べて１０倍程高い活性を示すため望ましい。 The metal oxide powder is not particularly limited as long as it has a photocatalytic function. FIG. 3 is a diagram comparing the amount of formic acid produced for various metal oxides. As shown in FIG. 3, it is particularly preferable to use titanium oxide or zinc oxide. These metal oxides are preferably in the form of fine particles in order to increase the contact surface area in the mixed solution. The average particle size of the fine particles is not particularly limited, but is, for example, 20 to 50 nm. In particular, the average particle size of the titanium oxide fine particles is preferably about 25 nm. Of the titanium oxide, the anatase type is desirable because it exhibits about 10 times higher activity than the rutile type.
本発明の一実施形態に係る蟻酸生成方法における具体的な反応プロセスは必ずしも明らかではないが、以下のように考えられる。まず、光触媒により、反応式（１）に示すように、水が分解され酸素と水素イオンと電子が生成される。
２Ｈ２Ｏ→Ｏ２＋４Ｈ＋＋４ｅ－ ・・・（１）
Although the specific reaction process in the formic acid production method according to the embodiment of the present invention is not always clear, it is considered as follows. First, as shown in the reaction formula (1), water is decomposed by the photocatalyst to generate oxygen, hydrogen ions and electrons.
2H 2 O → O 2 + 4H + + 4e -... ( 1)
次に、光触媒や色素等による光反応（人工光合成）プロセスを経て水素イオンと電子、及び二酸化炭素あるいは溶液に混合した有機物質から蟻酸が生成される（下記反応式（２）または反応式（３））。二酸化炭素はこの反応において必須ではない点に特徴を有する。この時、反応式（１）で生成した水素イオンと電子が消費される。また、反応式（２）によって二酸化炭素は、大気中及び／又は他の機関からの排ガス中に存在するものを利用することができるが、反応式（３）によって、溶液に混合した有機物質の炭素Ｃによってもギ酸が形成できる点に大きな特徴を有する。
ＣＯ２＋２Ｈ＋＋２ｅ－→ＨＣＯＯＨ ・・・（２）
有機物質＋２Ｈ＋＋２ｅ－→ＨＣＯＯＨ ・・・（３）
Next, formic acid is produced from hydrogen ions and electrons, and an organic substance mixed with carbon dioxide or a solution through a photoreaction (artificial photosynthesis) process using a photocatalyst, a dye, or the like (the following reaction formula (2) or reaction formula (3). )). Carbon dioxide is characterized in that it is not essential in this reaction. At this time, the hydrogen ions and electrons generated by the reaction formula (1) are consumed. Further, according to the reaction formula (2), carbon dioxide existing in the atmosphere and / or in the exhaust gas from other engines can be used, but according to the reaction formula (3), the organic substance mixed in the solution can be used. It has a great feature that formic acid can be formed even by carbon C.
CO 2 + 2H + + 2e- → HCOOH ・ ・ ・ (2)
Organic substance + 2H + + 2e- → HCOOH ・ ・ ・ (3)
この時、照射される光のうち、主に紫外線は光触媒としての金属酸化物に作用し、可視光は色素に作用するため、本発明の一態様に係る蟻酸生成方法では、その複合作用によって蟻酸の生成効率を倍増させていると考えられる。すなわち、金属酸化物と色素のみの場合であっても、金属酸化物と色素との相互作用により、直接、蟻酸生成反応へと電子を供与することも可能であると考えられる。 At this time, among the irradiated light, ultraviolet rays mainly act on the metal oxide as a photocatalyst, and visible light acts on the dye. Therefore, in the formic acid production method according to one aspect of the present invention, formic acid is produced by the combined action. It is considered that the production efficiency of is doubled. That is, even in the case of only the metal oxide and the dye, it is considered possible to directly donate electrons to the formic acid production reaction by the interaction between the metal oxide and the dye.
次に、本発明の一実施形態に係る蟻酸生成装置について説明する。図４は、本発明の一実施形態に係る蟻酸生成システムの一例を表す模式図である。本発明の一態様は、有機物質を含む溶液と光触媒機能を有する金属酸化物粉末を投入する原料投入部１１と、有機物質と金属酸化物粉末の混合溶液に対して太陽光又は光を照射して反応させる人工光合成反応部１２と、反応後の混合溶液から蟻酸を回収する蟻酸回収部１３を備えることを特徴とする蟻酸生成システム１０である。原料投入部１１と蟻酸回収部１３は同一容器であってもよい。
Next, the formic acid generator according to the embodiment of the present invention will be described. FIG. 4 is a schematic diagram showing an example of a formic acid production system according to an embodiment of the present invention. One aspect of the present invention is to irradiate a raw
原料投入部１１では、有機物質を含む溶液と光触媒機能を有する金属酸化物粉末を投入する。有機物質と金属酸化物粉末を混合した状態で投入してもよいし、別々に投入して混合するようにしてもよい。光触媒機能を有する金属酸化物粉末は、ほとんど消費されないため、初めに金属酸化物粉末を投入したのちは、有機物質のみを随時追加で投入する態様が考えられる。
In the raw
人工光合成反応部１２は、光化学反応装置として使用される。人工光合成反応部１２は、内部の混合溶液に太陽又は人工光源による光が照射されるように、透明な部材で構成することが好ましく、例えば、ガラス容器や透明なチューブ状ないし任意形状の筒状の部材が挙げられる。また、人工光合成反応部１２には、必要に応じて撹拌装置や送液用のポンプなどが備えられる。
The artificial
人工光合成反応部１２は、例えば、図４に示すように、光を透過するチューブ状ないし任意形状の筒状の部材であって、建物の屋根又は屋上に敷設され、混合溶液を部材内で循環させることにより人工光合成反応を行うようにしてもよい。このような構成とすることにより、例えば、住宅の屋根又は屋上等に設置することで、日中の太陽光を利用して蟻酸を生成し、ひいてはその蟻酸からエネルギーとしての水素を発生させることができる。
As shown in FIG. 4, for example, the artificial
蟻酸回収部１３では、人工光合成反応後の混合溶液から蟻酸を回収する。このようにして生成された蟻酸は、例えば濃縮されたのち、貯蔵設備等に貯蔵しておくこともできる。
The formic
以上説明したような、本発明の一実施形態に係る蟻酸生成システムは、以下に挙げるような利点を有する。
１．撹拌することは必須ではないが、高効率のためには、人工光合成に必要な材料がポンプ等を利用して溶液中を撹拌されながら動く方法が考えられ、その場合は、均一に太陽光が当たり、効率が高い。
２．従来の人工光合成反応装置は、ケースに入っているので、広大な面積での敷設やメンテナンスは容易ではなかったが、本発明の一態様では、太陽光のもとで、人工光合成材料を溶液として、例えば透明なホースに入れて流すだけなので、広い面積であっても、ホースを延長するだけで良く、敷設が格段に容易である。
３．発生した蟻酸の回収も、人工光合成材料の補充も、全て特定の箇所で可能となる。
４．全ての材料を単に投入補給することによって、人工光合成装置として半永久的に稼働できる。
The formic acid production system according to the embodiment of the present invention as described above has the following advantages.
1. 1. Stirring is not essential, but for high efficiency, a method is conceivable in which the material required for artificial photosynthesis moves while being agitated in the solution using a pump or the like, in which case sunlight is uniformly emitted. Hit and efficient.
2. 2. Since the conventional artificial photosynthesis reactor is contained in a case, it is not easy to lay and maintain it in a large area, but in one aspect of the present invention, the artificial photosynthesis material is used as a solution under sunlight. For example, since it is simply put in a transparent hose and flowed, it is only necessary to extend the hose even in a large area, and it is much easier to lay it.
3. 3. Recovery of generated formic acid and replenishment of artificial photosynthesis materials can all be performed at specific locations.
4. By simply adding and replenishing all the materials, it can operate semi-permanently as an artificial photosynthesis device.
以下、本発明について、実施例を用いてさらに具体的に説明するが、本発明は、以下の実施例に何ら限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples.
（実施例１）
酸化チタン粉末と、色素としてアントシアニンＢを用い、二酸化炭素の供給を全く行わずに、可視光を照射して時間経過による蟻酸生成量を測定した。結果を図５に示す。
(Example 1)
Using titanium oxide powder and anthocyanin B as a dye, the amount of formic acid produced over time was measured by irradiating with visible light without supplying carbon dioxide at all. The results are shown in FIG.
図５に示すように、３０時間までは照射時間に対応して蟻酸が生成されたが、３０時間を超えてからは、飽和し減少していくことが確認できた。これは、アントシアニンＢに含まれる有機物質の含有量に限りがあるためと推察される。 As shown in FIG. 5, it was confirmed that formic acid was produced corresponding to the irradiation time up to 30 hours, but after 30 hours, it was saturated and decreased. It is presumed that this is because the content of organic substances contained in anthocyanin B is limited.
（実施例２）
二酸化炭素の供給を全く行わずに、色素と、色素のない有機物との間で蟻酸生成量を測定した。ブドウ糖のみ、緑色素（試薬名：Fast Green）のみ、ブドウ糖＋緑色素の３パターンで測定した結果を図６に示す。
(Example 2)
The amount of formic acid produced between the dye and the non-dye organic matter was measured without any carbon dioxide supply. FIG. 6 shows the results of measurement with three patterns of glucose only, green pigment (reagent name: Fast Green) only, and glucose + green pigment.
図６に示すように、色素ではないブドウ糖であっても光照射によって蟻酸を効率よく生成できることが分かった。また、このような色素以外の有機物に色素を混合することで、複合作用が起き、蟻酸生成量が倍増した。すなわち、色素に、色素ではないブドウ糖を加えることで、ブドウ糖だけで得られる蟻酸の量の倍の量の蟻酸を生成できることが明らかとなった。 As shown in FIG. 6, it was found that formic acid can be efficiently produced by light irradiation even with glucose which is not a pigment. Further, by mixing the dye with an organic substance other than such a dye, a complex action occurred and the amount of formic acid produced was doubled. That is, it was clarified that by adding non-dye glucose to the pigment, formic acid can be produced in an amount twice as much as the amount of formic acid obtained by glucose alone.
（実施例３）
二酸化炭素の供給を全く行わない実験条件で、蟻酸生成システムにおける人工光合成法の耐久性について調べた。使用した酸化チタン２ｇに対して、アントシアニンＢの総投入量は０．８６ｇであった。酸化チタンを追加することなく、材料となる色素であるアントシアニンＢだけを毎日追加することで、６日間の光照射（ＨＩＤ）による蟻酸生成を実施した。結果を図７に示す。
(Example 3)
The durability of the artificial photosynthesis method in the formic acid production system was investigated under experimental conditions in which no carbon dioxide was supplied. The total amount of anthocyanin B added was 0.86 g with respect to 2 g of titanium oxide used. Formic acid production by light irradiation (HID) for 6 days was carried out by adding only the raw material anthocyanin B daily without adding titanium oxide. The results are shown in FIG.
図７に示すように、二酸化炭素の供給を全く行わない実験条件でも、本発明に係る蟻酸生成システムを適用することで酸化チタンの補給なく、材料となる色素の間歇的投入によって、連続して蟻酸生成ができることが明らかとなった。 As shown in FIG. 7, even under experimental conditions in which carbon dioxide is not supplied at all, by applying the formic acid production system according to the present invention, titanium oxide is not replenished, and the dye used as a material is continuously added. It became clear that formic acid can be produced.
（実施例４）
グルコース（ブドウ糖）と色素（緑色素）と酸化チタンの組み合わせによる混合溶液において、色素（緑色素）と酸化チタンの濃度をそれぞれ変化させて蟻酸生成速度を測定した。結果を図８に示す。
(Example 4)
In a mixed solution of glucose (dextrose), pigment (green pigment) and titanium oxide, the concentration of pigment (green pigment) and titanium oxide was changed and the formic acid production rate was measured. The results are shown in FIG.
図８に示すように、色素（緑色素）と酸化チタンの濃度については、蟻酸生成速度が最適となる濃度範囲が存在し、金属酸化物粉末（酸化チタン）濃度が８～１８％、色素（緑色素）が０．０２～０．１１％の時に高い蟻酸生成速度を有することが分かった。なお、酸化チタン濃度が１２％、緑色素濃度が０．０４％の時に最も高い蟻酸生成速度となった。 As shown in FIG. 8, regarding the concentrations of the dye (green dye) and titanium oxide, there is a concentration range in which the formic acid production rate is optimum, the metal oxide powder (titanium oxide) concentration is 8 to 18%, and the dye (dye) ( It was found that the green pigment) had a high rate of formic acid production when it was 0.02 to 0.11%. The highest formic acid production rate was obtained when the titanium oxide concentration was 12% and the green pigment concentration was 0.04%.
（実施例５）
グルコースのみ、グルコース＋緑色素＋炭素パウダー、グルコース＋炭素パウダーのみの３種類を用いた場合の、生成する蟻酸濃度の経時変化を測定した。結果を図９に示す。
(Example 5)
The time course of the formic acid concentration produced was measured when only glucose, glucose + green pigment + carbon powder, and glucose + carbon powder were used. The results are shown in FIG.
図９に示すように、炭素パウダー（活性炭パウダー）のみの使用において、色素の添加の場合と同等、又はそれ以上の効果があることが判明した。 As shown in FIG. 9, it was found that the use of carbon powder (activated carbon powder) alone has the same or higher effect than the addition of the dye.
（実施例６）
色素（緑色素）を用いた場合と、炭素パウダー（活性炭）を用いた場合に、光源（白色光、紫外光）を変えた時の蟻酸生成速度の波長依存性を調べた。なお、紫外光は酸化チタンの吸収光である３６５ｎｍである。色素（緑色素）を用いた場合の結果を図１０に、炭素パウダー（活性炭）を用いた場合の結果を図１１に示す。
(Example 6)
The wavelength dependence of the formic acid production rate when the light source (white light, ultraviolet light) was changed was investigated when the dye (green dye) was used and when the carbon powder (activated carbon) was used. The ultraviolet light is 365 nm, which is the absorbed light of titanium oxide. The result when the dye (green dye) is used is shown in FIG. 10, and the result when the carbon powder (activated carbon) is used is shown in FIG.
図１０、図１１ともに、紫外光を含む光源の時に蟻酸生成速度が大きくなり、白色光＋紫外光の光が一番大きな生成速度を示している。特に炭素パウダー（活性炭）を用いた場合（図１１）には、紫外光を単独で照射した後の光照射で蟻酸の生成速度が大きく向上した。 In both FIGS. 10 and 11, the formic acid production rate is high when the light source contains ultraviolet light, and the white light + ultraviolet light has the highest production rate. In particular, when carbon powder (activated carbon) was used (FIG. 11), the rate of formic acid production was greatly improved by light irradiation after irradiation with ultraviolet light alone.
以上の通り、本発明の各実施形態及び各実施例について詳細に説明したが、本発明の新規事項及び効果から実体的に逸脱しない多くの変形が可能であることは、当業者には、容易に理解できるであろう。従って、このような変形例は、全て本発明の範囲に含まれるものとする。 As described above, each embodiment and each embodiment of the present invention have been described in detail, but it is easy for those skilled in the art to be able to make many modifications that do not substantially deviate from the new matters and effects of the present invention. You can understand. Therefore, all such modifications are included in the scope of the present invention.
例えば、明細書又は図面において、少なくとも一度、より広義又は同義な異なる用語と共に記載された用語は、明細書又は図面のいかなる箇所においても、その異なる用語に置き換えることができる。また、蟻酸生成方法及び蟻酸生成システムの構成も本発明の各実施形態及び各実施例で説明したものに限定されず、種々の変形実施が可能である。 For example, in a specification or drawing, a term described at least once with a different term having a broader meaning or a synonym may be replaced with the different term in any part of the specification or the drawing. Further, the formic acid production method and the configuration of the formic acid production system are not limited to those described in each embodiment and each embodiment of the present invention, and various modifications can be carried out.
１０ 蟻酸生成システム、１１ 原料投入部、１２ 人工光合成反応部、１３ 蟻酸回収部 10 Formic acid generation system, 11 Raw material input section, 12 Artificial photosynthesis reaction section, 13 Formic acid recovery section
Claims (8)
前記有機物質と前記金属酸化物粉末の混合溶液に対して太陽光又は光を照射して反応させる工程と、
反応後の前記混合溶液から蟻酸を回収する工程
を有し、
前記混合溶液は炭素パウダーを含むことを特徴とする蟻酸生成方法。 The process of mixing a solution containing an organic substance and a metal oxide powder having a photocatalytic function,
A step of irradiating a mixed solution of the organic substance and the metal oxide powder with sunlight or light to cause a reaction.
Step of recovering formic acid from the mixed solution after the reaction
Have,
A method for producing formic acid, wherein the mixed solution contains carbon powder .
該混合溶液に太陽光を照射することによって蟻酸の生成反応を行うことを特徴とする請求項１乃至請求項５のいずれか１項に記載の蟻酸生成方法。 Circulate the mixed solution and
The formic acid production method according to any one of claims 1 to 5 , wherein the formic acid production reaction is carried out by irradiating the mixed solution with sunlight.
前記有機物質と前記金属酸化物粉末の混合溶液に対して太陽光又は光を照射して反応させる人工光合成反応部と、
反応後の前記混合溶液から蟻酸を回収する蟻酸回収部
を備え、
前記混合溶液は炭素パウダーを含むことを特徴とする蟻酸生成システム。 A raw material input section for charging a solution containing an organic substance and a metal oxide powder having a photocatalytic function,
An artificial photosynthesis reaction unit that irradiates a mixed solution of the organic substance and the metal oxide powder with sunlight or light to react.
A formic acid recovery unit for recovering formic acid from the mixed solution after the reaction is provided.
The formic acid production system , wherein the mixed solution contains carbon powder .
前記混合溶液を前記部材内で循環させることにより前記人工光合成反応を行うことを特徴とする請求項７に記載の蟻酸生成システム。 The artificial photosynthesis reaction unit is a tubular or arbitrary-shaped tubular member that transmits light, and is laid on the roof or roof of a building.
The formic acid production system according to claim 7 , wherein the artificial photosynthesis reaction is carried out by circulating the mixed solution in the member.
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| JP2002079275A (en) | 2000-09-08 | 2002-03-19 | Matsushita Electric Ind Co Ltd | Water cleaning device |
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